Conductive nanofibers of poly(vinylidene fluoride) (PVDF) filled with polyaniline (PANi)-coated multi-wall carbon nanotubes (MWCNTs) were fabricated using the electrospinning technique. PANi is an intrinsically conductive polymer. The addition of PANi-coated MWCNTs to PVDF created short conductive strands on the surface of the nanofibers, facilitating the formation of a conductive network in the transverse direction of the nanofibers. Piezoelectricity along with electric conductivity makes these PVDF nanofibers promising for applications such as sensors and actuators. Electrospun PVDF nanofiber mats had higher piezoelectricity than melt-processed samples produced using traditional polymer processing techniques, such as compression molding. Spectroscopic imaging techniques were employed to study the effects of the filler and processing conditions on the nanofiber structure. X-ray diffraction, Fourier transform infrared spectroscopy and differential scanning calorimetry results indicated a large increase in the -phase crystals of the PVDF nanofibers. This higher content of -phase crystals enhanced the piezoelectricity of the nanofibers. (c) 2015 Society of Chemical Industry